Absorption of sulfur compounds from gas streams

ABSTRACT

Hydrogen sulfide and lower alkyl mercaptans are selectively extracted from a gas stream by contacting the stream with piperazinone or an alkyl substituted piperazinone which may contain a substantial proportion of water. The absorbed sulfur compounds can be regenerated by heating the extraction liquid to about 85°-150° C.

BACKGROUND OF THE INVENTION

This invention relates to a method for selectively removing H₂ S and lower alkyl mercaptans from gaseous streams. More particularly, it relates to a method whereby these sulfur compounds are selectively removed by contacting the gas stream with a liquid piperazinone compound.

Gas streams consisting largely of methane, other lower aliphatic hydrocarbons, hydrogen, and other gases such as natural gas, refinery gases, and coal gasification product streams typically contain acidic contaminants such as H₂ S, lower alkyl mercaptans, other sulfur compounds, and CO₂. It is desirable to separate the H₂ S and any mercaptans that may be present while leaving the CO₂ largely in the gas stream so as to obtain a stream of high H₂ S content for efficient sulfur recovery in a Claus plant or other such sulfur recovery process. Known sour gas purification solvents include ethanolamine, N-methyldiethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, sulfolane, N-methyl-3-morpholinone, their aqueous solutions, and mixtures of these. While these are effective absorbents for H₂ S, they typically show only kinetic selectivity. Substantial quantities of CO₂ will also be absorbed when it is present.

SUMMARY OF THE INVENTION

It has now been found that the sulfur compounds H₂ S and lower alkyl mercaptans in particular are selectively absorbed from a gaseous feed stream in the presence of CO₂ when the gaseous feed stream is contacted with a liquid piperazinone compound of the formula ##STR1## wherein each R, R', and R" is independently a hydrogen atom or a lower alkyl group. The piperazinone compound can be used in anhydrous or essentially anhydrous state or it may be combined with water to about 45 percent piperazinone concentration. The liquid piperazinone compound absorption medium thus contacted with the gaseous feed stream forms a mixture rich in H₂ S and mercaptans if present and these sulfur compounds are efficiently and essentially completely desorbed by heating the absorption medium to about 85° C.-150° C. The absorption step can be carried out at any convenient temperature below about 60° C. where the absorption medium remains liquid. Preferably, the absorption is done at about 15° C.-50° C.

DETAILED DESCRIPTION OF THE INVENTION

Piperazinone compounds of the invention can be prepared by any of several known methods, see particularly Strong et al., U.S. Pat. Nos. 2,649,450 and 2,700,668.

1,4-Dialkylpiperazinones, and particularly 1,4-dimethylpiperazinone, are preferred. The term "lower alkyl" in the above general formula is defined as meaning alkyl of 1-5 carbon atoms such as methyl, ethyl, isopropyl, tert-butyl, and tert-amyl. Other preferred piperazinones include 3-methylpiperazinone, 4-ethylpiperazinone, 3,3,4-trimethylpiperazinone, 1-ethyl-4-methylpiperazinone, and 1-tert-butyl-4-methylpiperazinone.

The piperazinone absorption medium may contain up to about 55 percent of water. Best results are obtained when less than an equal weight of water is present, for example, from about 75 percent aqueous piperazinone to the anhydrous or nearly anhydrous material. Since these piperazinones are hygroscopic and most gas streams of the kind treated by this process normally contain more or less water vapor, in practice, there is almost always some water present in the absorption medium as the absorption process proceeds even when the medium is initially essentially anhydrous.

The class of piperazinone compounds described herein effectively promote the hydrolysis of carbon oxysulfide to H₂ S and CO₂ in the presence of water as set forth in application Ser. No. 778,903 of J. W. Bozzelli, D. M. Bremer, and G. D. Shier filed concurrently herewith, the disclosure of which is hereby incorporated by reference. Therefore, the H₂ S absorption and the COS hydrolysis can be combined in a single contacting step. Alternatively, a COS-containing gas can be contacted with a liquid aqueous piperazinone compound in a first stage as described in the above application or with another COS-hydrolyzing solution to hydrolyze at least the major part of the COS and absorb at least some of the H₂ S and mercaptans present, then the gas purification process is completed in a second stage using a piperazinone absorption medium as described herein.

The absorption process may be run at or slightly above atmospheric pressure and in some cases, it may be advantageous to employ superatmospheric pressure as high as 10,000 psi to increase the rate or amount of absorption. The time of contact during the absorption step can vary from about a few seconds up to about 1 hour.

Regeneration of the absorbed sulfur compounds is readily accomplished by heating the enriched solvent to 85° C. or above, preferably to 100° C.-150° C. Moderately reduced pressure can be applied to accelerate the desorption to some extent although this is usually not necessary. The piperazinone absorption solvent is further characterized by its ready release of nearly all of the absorbed sulfur compounds upon heating, 90 percent or more of the absorbed H₂ S and mercaptans being thus desorbed in a relatively short time as compared to known alkanolamine absorbents.

Further advantages of the piperazinone compound absorption media of this invention in addition to those noted above include a desirable low viscosity and high degrees of chemical and thermal stability. Its unique selectivity for H₂ S in the presence of CO₂ is of particular interest. Whereas some known sour gas purification solvents show some selectivity toward H₂ S when both H₂ S and CO₂ are present, these piperazinone compound media exhibit nearly complete equilibrium H₂ S selectively over CO₂ at atmospheric and superatmospheric pressure.

EXAMPLE 1

The absorption of H₂ S and CO₂ in different alkaline solvents was estimated by atomizing a known amount of a solvent into a suction flask filled with H₂ S or CO₂ at atmospheric pressure and following the pressure reduction in the flask by means of an automatic pressure recorder. Measurements were made at 22° C. The pressure reading at 2 minutes after injection of the solvent was used to estimate the quantity of gas absorbed. This is a qualitative test useful for rough screening. Since the results are obtained at reduced pressure, these results are low as compared to those found in practical gas scrubbing where superatmospheric pressure is the usual condition. The results of these tests are listed in Table I.

                  TABLE I                                                          ______________________________________                                                                   g. Gas Absorbed                                                     Gas        per 100 g.                                           Solvent        Injected   Solvent                                              ______________________________________                                         45% NNDP.sup.(1)                                                               55% H.sub.2 O  H.sub.2 S  trace                                                100% NNDP.sup.(1)                                                                             H.sub.2 S  4.6                                                  50% 3-(dimethyl-                                                                amino)-1,2-   H.sub.2 S  8.0                                                  propanediol                                                                    50% H.sub.2 O                                                                  50% MDEA.sup.(2)                                                               50% H.sub.2 O  H.sub.2 S  5.3                                                  45% NNDP.sup.(1)                                                                              CO.sub.2   no absorption                                        55% H.sub.2 O                                                                  90% NNDP.sup.(1)                                                                              CO.sub.2   no absorption                                        10% H.sub.2 O                                                                  50% 3-(dimethyl-                                                                amino)-1,2-   CO.sub.2   3.9                                                  propanediol                                                                    50% H.sub.2 O                                                                  50% MDEA.sup.(2)                                                               50% H.sub.2 0  CO.sub.2   1.4                                                  ______________________________________                                          Terms:-                                                                        .sup.(1) NNDP = 1,4-dimethylpiperazinone                                       .sup.(2) MDEA = N-methyldiethanolamine                                   

EXAMPLE 2

The efficiency with which absorbed H₂ S can be liberated from a solvent was measured by first saturating a 50 g sample by bubbling H₂ S through a 19 gauge needle immersed in the solvent for 2 hours, then stripping off the H₂ S from the saturated solvent by heating it to 105° C. as fast as possible. A magnetic stirbar was used for agitation. The heating was done using the same equipment and procedure in each case. Results are listed in Table II.

                  TABLE II                                                         ______________________________________                                                               Wt. % H.sub.2 S.sup.(2)                                            Wt. % H.sub.2 S.sup.(2)                                                                    in Solvent  Time to                                                in Saturated                                                                               after Regen-                                                                               105° C,                               Solvent   Solvent     eration     min.                                         ______________________________________                                         95% NNDP                                                                        5% H.sub.2 O                                                                            3.63        0.38        7                                            30% MEA.sup.(1)                                                                70% H.sub.2 O                                                                            13.71       2.61        16                                           50% MDEA                                                                       50% H.sub.2 O                                                                            8.15        1.81        12                                           ______________________________________                                          .sup.(1) MEA = monoethanolamine                                                .sup.(2) Based on the amine content                                       

We claim:
 1. A process for removing sulfur compounds of the group H₂ S and lower alkyl mercaptans from a gaseous stream which comprises contacting said stream with a liquid piperazinone compound of the formula ##STR2## wherein each R, R', and R" is independently a hydrogen atom or a lower alkyl group, thereby forming a mixture of said piperazinone rich in H₂ S and alkyl mercaptans.
 2. The process of claim 1 wherein the absorbed H₂ S and mercaptans are desorbed by heating the enriched piperazinone compound to about 85° C.-150° C.
 3. The process of claim 1 wherein the piperazinone compound is 1,4-dimethylpiperazinone.
 4. The process of claim 1 wherein the liquid piperazinone compound is present as its aqueous solution in about 45 to 99 percent concentration.
 5. The process of claim 4 wherein the gaseous feed stream is contacted with the aqueous piperazinone compound at a temperature of about 15° C.-60° C.
 6. The process of claim 4 wherein the gaseous feed stream is contacted with the aqueous piperazinone compound under superatmospheric pressure. 